WO1996028518A1 - Pigment ink for ink jet printer - Google Patents

Pigment ink for ink jet printer Download PDF

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Publication number
WO1996028518A1
WO1996028518A1 PCT/JP1996/000696 JP9600696W WO9628518A1 WO 1996028518 A1 WO1996028518 A1 WO 1996028518A1 JP 9600696 W JP9600696 W JP 9600696W WO 9628518 A1 WO9628518 A1 WO 9628518A1
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WIPO (PCT)
Prior art keywords
ink
pigment
jet printer
water
ink jet
Prior art date
Application number
PCT/JP1996/000696
Other languages
French (fr)
Japanese (ja)
Inventor
Chiaki Sekioka
Kohei Kiyota
Masaru Sugie
Original Assignee
Fujitsu Isotec Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujitsu Isotec Limited filed Critical Fujitsu Isotec Limited
Priority to JP52748396A priority Critical patent/JP3625479B2/en
Priority to GB9623811A priority patent/GB2303376B/en
Priority to DE19680301T priority patent/DE19680301C2/en
Publication of WO1996028518A1 publication Critical patent/WO1996028518A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00—Lakes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to an aqueous ink jet printer ink for low viscosity, high dispersibility, and containing a high concentration of pigment.
  • the printing ink includes a solution ink in which a dye is dissolved in a solvent as a colorant and a pigment ink in which a solid pigment is dispersed in a liquid as a colorant.
  • Pigment-based inks are generally conventional inks that do not fade, retain a more robust color, and are more vivid than dye-based inks.
  • Dye-based inks are the mainstream inks for use, but they have problems in bleeding, light resistance, water resistance, and the like, and the use of pigment-based inks is desired. In order to solve this problem, as described in Japanese Patent Application Laid-Open Nos.
  • An object of the present invention is to provide an ink having a relatively low viscosity, high dispersibility, and containing a high concentration of pigment.
  • a polymer material that is insoluble or hardly soluble in water is used.
  • An ink for an ink jet printer comprises water, a pigment, and a water-insoluble or hardly soluble and hydrophilic polymer material, and the pigment is insoluble or hardly soluble in the water. It is characterized by being coated with a hydrophilic polymer material.
  • This ink is insoluble or hardly soluble in water and hydrophilic, such as, for example, isobutylene maleic anhydride copolymer resin, copolymerized nylon, polyvinylisobutyl ether, polyvinylethyl ether.
  • the polymer material is dissolved in an organic solvent compatible with water, such as THF (tetrahydrofuran), DMF (dimethylformamide), etc., and the bead mill is added by adding a face mask. It is manufactured by evaporating the organic solvent after dispersing by the method described above.
  • the pigment by coating the pigment with a hydrophilic polymer material that is insoluble or hardly soluble in water, the dispersibility of the pigment is improved, and as a result, sedimentation of the pigment can be prevented. . Further, since the high tackiness of such a polymer material itself is high, a printing medium such as printing paper is used. It can improve fixation to the body.
  • the inks of the present invention can further include a UV curable monomer or an oligomer.
  • the inks of the present invention including curable monomers or oligomers, can be instantly exposed to ultraviolet light (eg, 10 mW / cm 2 ) after printing on media (paper). It can cure and fix the ligomer. Because such inks contain low viscosity monomers or oligomers, they generally have low viscosity and will not cure unless exposed to ultraviolet light. This has the advantage that clogging on the head does not occur.
  • the UV curable monomer or oligomer can be any conventional UV curable monomer or oligomer, such as Nippon Kayaku's TMPTA, DPHA, D-31 0, D-330, MANDA (trade name) and the like. Each of these has the following chemical formula:
  • Pigments useful in the present invention include any of the inorganic and organic pigments used in conventional pigmented inks, such as carbon black, alumina, barium sulfate, graphite, titanium white, and the like. Includes synthetic inorganic pigments and synthetic organic pigments such as azo pigments, lake pigments from basic dyes and phthalocyanine pigments. Furthermore, various metals and their oxides can also be used as pigments.
  • Useful particle sizes for the pigments are between 0.01 and 1 micron, preferably between 0.01 and 0.5 micron.
  • the pigment in the case of an organic pigment, is a force that can be contained at a content of up to about 10% by weight of the entire ink composition, and generally ranges from 1% by weight to 5% by weight. This is preferred. If inorganic pigments are used, they can contain up to about 20% by weight, and generally range from 3% to 10% by weight.
  • Example 2 In a bead mill connected to a temperature controller, at 40 ° C, water 92 g and 8 g of the same pigment used in Example 1 were added and dispersed for about 15 minutes until the particle size became 0.5 ⁇ m or less.
  • the ink manufactured in this way is called distributed ink B.
  • Example 1 and Comparative Example 1 produced as described above were stored in sample bottles at 5 ° C. and 40 ° C. for three months, respectively.
  • Each sample was stored for 3 months at 15 ° C to 70 ° C in a sample bottle.
  • the following tests 3 to 6 were performed using a thermal ink jet type jet printer of FMJP 201 (manufactured by Fujitsu Limited).
  • the ink produced in Example 2 was cured for 1 second at an intensity of 10 mw / cm 2 using an ultraviolet lamp.
  • Test pieces were printed on commercially available recycled paper (WR paper manufactured by Xerox Corporation) and measured with a Macbeth densitometer.
  • Fujitsu's general-purpose ink jet printer was used, but similar results can be obtained with other thermal printers and piezo-type ink jet printers. it is conceivable that. Industrial applicability
  • an aqueous dispersion of the coated pigment has stability, and At the time of printing, the fixability to a medium (paper) can be improved due to the adhesiveness of the polymer material.
  • the viscosity of the ink as a whole can be reduced, and it will not cure unless irradiated with ultraviolet light. No clogging occurs.
  • a pigment ink instead of a dye ink, printing can be performed with a pigment ink having excellent water resistance and light fastness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

An ink for an ink jet printer, characterized by comprising water, a pigment, and a polymeric material which is insoluble or sparingly soluble in water and hydrophilic, the pigment being coated with the polymeric material which is insoluble or sparingly soluble in water and hydrophilic. The ink is produced by, for example, dissolving a polymeric material which is insoluble or sparingly soluble in water and hydrophilic, such as an isobutylene/maleic anhydride copolymer resin, a nylon copolymer, polyvinyl isobutyl ether, or polyvinyl ethyl ether, in an organic solvent compatible with water, such as THF (tetrahydrofuran) or DMF (dimethylformamide), adding a pigment to the resulting solution, dispersing the mixture by means of a bead mill or the like, and evaporating the organic solvent.

Description

明 細 書 イ ンク ジヱ ッ トプリ ンター用顔料系イ ンク 技術分野  Description Ink jet pigment pigment ink for printers Technical field
本発明は、 低粘度で、 分散性が高く 、 そ して高濃度の顔料を含有 する水性のィ ン ク ジ ェ ッ トプリ ン タ 一用ィ ン クに関する。 背景技術  The present invention relates to an aqueous ink jet printer ink for low viscosity, high dispersibility, and containing a high concentration of pigment. Background art
印刷イ ンクには着色剤と して染料を溶剤に溶解させた溶液系イ ン ク と着色剤と して固体の顔料を液体中に分散させた顔料系イ ンクが ある。 顔料系イ ン クは、 一般に、 染料系イ ンク と比較して、 褪色せ ず、 堅牢な色を保持するこ とができ、 そ して鮮やかさに傻れている 従来のィ ンク ジュ ッ ト用イ ンクは、 染料系ィ ンクが主流であるが 、 これは、 滲み、 耐光性及び耐水性等に問題があり、 顔料系イ ン ク の使用が望まれている。 この問題を解決するために、 特開昭 6 1 — 2 8 3 8 7 5 、 特開昭 6 4 — 6 0 7 4及び特開平 1 — 3 1 8 8 1 号 公報に記載されているように、 力一ボンブラ ッ ク、 ァニリ ンブラ ッ ク等のような顔料を用いたイ ンクが考案されている。 しかし、 これ らに記載されている顔料含有イ ン クは、 記録媒体 （例えば、 紙） へ の定着性が低く 、 また、 高濃度の顔料を含有させると液体中でイ ン クが凝集し、 沈降するといつた欠点があった。 このため、 イ ン ク ジ ヱ ッ トプリ ンター用イ ンクでは顔料の濃度を低く しなければならな かった。 紙への定着性を向上させ、 また、 粒子の分散を安定化させ るためのイ ンク ジエ ツ トプリ ンター用イ ンクは特開平 5 — 3 3 1 3 9 5号公報に開示されている。 この公報に開示されているイ ンクは 水、 着色剤及び水溶性高分子、 例えば、 ポ リ ビニルアルコールを含 む。 発明の開示 The printing ink includes a solution ink in which a dye is dissolved in a solvent as a colorant and a pigment ink in which a solid pigment is dispersed in a liquid as a colorant. Pigment-based inks are generally conventional inks that do not fade, retain a more robust color, and are more vivid than dye-based inks. Dye-based inks are the mainstream inks for use, but they have problems in bleeding, light resistance, water resistance, and the like, and the use of pigment-based inks is desired. In order to solve this problem, as described in Japanese Patent Application Laid-Open Nos. Sho 61-283875, JP-A-64-7044 and JP-A-1-31881, Inks using pigments such as bonbon black and aniline black have been devised. However, the pigment-containing inks described in these publications have low fixability to a recording medium (for example, paper), and when a high concentration of pigment is contained, the ink aggregates in a liquid, There was a disadvantage when it settled. For this reason, the ink concentration for the ink jet printer had to be lowered. An ink for an inkjet printer for improving the fixing property to paper and stabilizing the dispersion of particles is disclosed in JP-A-5-313395. The ink disclosed in this publication is Contains water, colorants and water-soluble polymers, such as polyvinyl alcohol. Disclosure of the invention
ノ ズルの閉塞等を回避するために、 更に低粘度で分散性の高い顔 料系イ ンクが望まれている。 本発明の目的は、 比較的に低粘度で、 分散性が高く 、 高濃度の顔料を含有するイ ン クを提供するこ とであ る。 本発明のイ ンクでは、 水に不溶性又は難溶性の高分子材料を使 用するために、 高分子材料が分散系全体に分布せず、 顔料の周囲を コー ト した形になるので、 低粘度で、 分散性が高く 、 しかも顔料濃 度の高いイ ンクを提供することが可能である。  In order to avoid clogging of nozzles and the like, pigment inks having lower viscosity and higher dispersibility are desired. An object of the present invention is to provide an ink having a relatively low viscosity, high dispersibility, and containing a high concentration of pigment. In the ink of the present invention, a polymer material that is insoluble or hardly soluble in water is used. Thus, it is possible to provide an ink having a high dispersibility and a high pigment concentration.
本発明のイ ンク ジヱ ッ トプリ ンター用イ ンクは、 水、 顔料、 及び 、 水に不溶性又は難溶性で且つ親水性の高分子材料からなり、 前記 顔料が前記水に不溶性又は難溶性で且つ親水性の高分子材料により コ一 卜されているこ とを特徴とする。 発明を実施するための最良の形態  An ink for an ink jet printer according to the present invention comprises water, a pigment, and a water-insoluble or hardly soluble and hydrophilic polymer material, and the pigment is insoluble or hardly soluble in the water. It is characterized by being coated with a hydrophilic polymer material. BEST MODE FOR CARRYING OUT THE INVENTION
このイ ンク は、 例えば、 イ ソブチ レ ン無水マ レイ ン酸共重合樹脂 、 共重合ナイ ロ ン、 ポ リ ビニルイ ソブチルエーテル、 ポ リ ビニルェ チルエーテルのような水に不溶性又は難溶性で且つ親水性の高分子 材料を、 T H F (テ ト ラ ヒ ドロ フ ラ ン） 、 D M F (ジメ チルホルム ア ミ ド） 等のような水と相溶性の有機溶剤に溶解させ、 その後、 顔 枓を添加してビーズミ ル等で分散させた後、 有機溶剤を蒸散させる こ とにより製造される。 このようにして、 顔料を水に不溶性又は難 溶性で且つ親水性の高分子材料で被覆するこ とにより、 顔料の分散 性を向上させ、 結果と して顔料の沈降を防ぐこ とができ る。 更に、 このような高分子材料自体の粘着性が高いため、 印刷紙等の印字媒 体への定着性を向上させるこ とができる。 This ink is insoluble or hardly soluble in water and hydrophilic, such as, for example, isobutylene maleic anhydride copolymer resin, copolymerized nylon, polyvinylisobutyl ether, polyvinylethyl ether. The polymer material is dissolved in an organic solvent compatible with water, such as THF (tetrahydrofuran), DMF (dimethylformamide), etc., and the bead mill is added by adding a face mask. It is manufactured by evaporating the organic solvent after dispersing by the method described above. In this way, by coating the pigment with a hydrophilic polymer material that is insoluble or hardly soluble in water, the dispersibility of the pigment is improved, and as a result, sedimentation of the pigment can be prevented. . Further, since the high tackiness of such a polymer material itself is high, a printing medium such as printing paper is used. It can improve fixation to the body.
本発明のイ ンクは更に紫外線硬化性モノ マー若し く はオ リ ゴマー を含むこ とができる。 硬化性モノ マー若し く はオリ ゴマーを含む本 発明のイ ンクは媒体 （紙） への印字後に紫外線ラ ンプ （例えば、 1 0 mW/ c m 2 ) で瞬時にモノ マ一若し く はオ リ ゴマーを硬化させ て定着させるこ とができる。 このようなイ ンクは、 低粘度のモノ マ 一若し く はオリ ゴマーを含むこ とから、 全体と して、 粘度が低く な り、 そ して紫外線を照射しないかぎり硬化しないこ とからへッ ド上 での目詰ま りを生じないという利点を有する。 紫外線硬化性モノ マ 一若し く はオ リ ゴマーは通常のあらゆる紫外線硬化性モ ノ マー若し く はオリ ゴマーであってよ く 、 例えば、 日本化薬製の T M P T A , D P H A , D— 3 1 0， D - 3 3 0， M A N D A (商品名） 等が挙 げられる。 これらはそれぞれ下記の化学式を有する。 The inks of the present invention can further include a UV curable monomer or an oligomer. The inks of the present invention, including curable monomers or oligomers, can be instantly exposed to ultraviolet light (eg, 10 mW / cm 2 ) after printing on media (paper). It can cure and fix the ligomer. Because such inks contain low viscosity monomers or oligomers, they generally have low viscosity and will not cure unless exposed to ultraviolet light. This has the advantage that clogging on the head does not occur. The UV curable monomer or oligomer can be any conventional UV curable monomer or oligomer, such as Nippon Kayaku's TMPTA, DPHA, D-31 0, D-330, MANDA (trade name) and the like. Each of these has the following chemical formula:
T M P T A T M P T A
0  0
II II
CH20CCH= CH2 CH 2 0CCH = CH 2
0  0
II II
CH2CH2- C- CH20CCH= CH: CH 2 CH 2 -C- CH 2 0 CCH = CH:
I I
CH20CCH= CH2 CH 2 0CCH = CH 2
II  II
o  o
D P H A , D - 3 1 0 , D - 3 3 0 D P H A, D-3 10, D-3 3 0
R0CH2 - 20RR0CH 2 - 2 0R
Figure imgf000005_0001
Figure imgf000005_0001
(上式中、 Rが全てァク リ ロイルである化合物と Rの う ちの 5個が ァク リ ロイルであり且つ Rのうちの 1 個力くヒ ドロキシである化合物 の混合物である力、、 Rのうちの 5個がァク リ ロイルであり且つ尺の うちの 1 個がアルキノ ィルである力、、 または Rのう ちの 3個がァク リ ロイルであり且つ Rのう ちの 3個がアルキノ ィルである。 ） (In the above formula, a compound in which R is all acryloyl and a compound in which 5 of Rs are acryloyl and one of R is strongly hydroxy A force that is a mixture of the following, a force where 5 of R are acryloyl and one of the scales is alkynyl, or 3 of R are acryloyl And three of the R are alkynyls. )
M A N D A M A N D A
0  0
II II
CH2 = CHCOCH2 CH 2 = CHCOCH2
CH3 - C- CH3 CH3 0 CH 3 -C- CH 3 CH 3 0
I I II I I II
CH，0C - C- CH, = CHCOCH, CH, 0C-C- CH, = CHCOCH,
II I  II I
0 CH3 紫外線硬化のための重合開始剤と しては 2， 4 — ジェチルチオキ サン ト ン及びべンゾフ ヱ ノ ンのような通常の開始剤を使用するこ と ができる。 0 As a polymerization initiator for UV curing of CH 3, ordinary initiators such as 2,4-diethylthioxanthone and benzophenone can be used.
本発明に有用な顔料は通常の顔料系イ ンクに使用されるあらゆる 無機及び有機顔料を含み、 例えば、 カーボンブラ ッ ク、 アル ミ ナ、 硫酸バリ ウム、 黄鉛、 チタ ンホワイ 卜等のような合成無機顔料、 及 び、 ァゾ顔料、 塩基性染料からのレーキ顔料及びフ タ ロ シアニ ン顔 料等のような合成有機顔料を含む。 更に、 種々の金属およびその酸 化物等を顔料と して使用する こ と もでき る。  Pigments useful in the present invention include any of the inorganic and organic pigments used in conventional pigmented inks, such as carbon black, alumina, barium sulfate, graphite, titanium white, and the like. Includes synthetic inorganic pigments and synthetic organic pigments such as azo pigments, lake pigments from basic dyes and phthalocyanine pigments. Furthermore, various metals and their oxides can also be used as pigments.
顔料の有用な粒子サイズは 0. 0 1 〜 1 ミ ク ロ ンであり、 特に 0 . 0 1 - 0. 5 ミ ク ロ ンであるこ とが好ま しい。  Useful particle sizes for the pigments are between 0.01 and 1 micron, preferably between 0.01 and 0.5 micron.
本発明のイ ンクにおいて、 顔料は、 有機顔料の場合、 イ ンク組成 物全体の約 1 0重量％までの含有率で含むこ とができる力 一般に は 1 重量％~ 5重量％の範囲である こ とが好ま しい。 無機顔料を使 用する場合には、 約 2 0重量％までを含むこ とができ、 一般には 3 重量％〜 1 0重量％の範囲である。 実施例 In the ink of the present invention, in the case of an organic pigment, the pigment is a force that can be contained at a content of up to about 10% by weight of the entire ink composition, and generally ranges from 1% by weight to 5% by weight. This is preferred. If inorganic pigments are used, they can contain up to about 20% by weight, and generally range from 3% to 10% by weight. Example
以下の実施例により本発明を更に詳細に説明するが、 本発明はこ れらの実施例に限定されるものではない。  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例 1 Example 1
温度制御装置を備えたビーズミ ルに、 4 0 °Cにおいて、 T H F ( テ ト ラ ヒ ドロフ ラ ン） 1 0 0 g、 顔料 （ミ ツビシカーボン # 2 3 0 0 ) 8 g、 イ ソブチレン無水マレイ ン酸共重合樹脂 1 2 gを加え、 粒径が 0. 5 m以下になるまで、 約 1 5分間分散させた。 このよ う に得られた分散液 （ 1 2 0 g ) を溶剤分離装置 （蒸留塔） に入れ 、 更に蒸留水 1 0 0 0 gを加え、 加熱攪拌するこ とにより乳化させ 、 そ して T H Fを蒸発させて水に対する T H Fの含有率を 0. 0 1 %以下と し、 水の含有量が 8 0 gになるまで蒸発させた。 このよう に得られたイ ンクを分散イ ンク Aと呼ぶ。  In a bead mill equipped with a temperature controller, at 40 ° C, 100 g of THF (tetrahydrofuran), 8 g of pigment (MITSUBISHI CARBON # 230), 8 g of isobutylene maleic anhydride 12 g of the copolymer resin was added and dispersed for about 15 minutes until the particle size became 0.5 m or less. The thus obtained dispersion (120 g) was put into a solvent separator (distillation column), further added with 100 g of distilled water, emulsified by heating and stirring, and then THF. Was evaporated to a THF content of less than 0.01%, and evaporated until the water content was 80 g. The ink thus obtained is referred to as distributed ink A.
上記の分散イ ンク A 5 0重量部、 蒸留水 4 0重量部、 ジエチ レ ン グリ コール 5重量部及びエチルアルコール 5重量部を、 スー パ ー ミ ル分散機 （井上製作所） で攪拌混合し、 その後 0. 5 / mのフ ィ ル ターで濾過してイ ンクを製造した。 このイ ンクの粘度は 2 0 °Cにお いて 2. 8 c pであり、 顔料濃度は 4重量％であった。  50 parts by weight of the above dispersion ink A, 40 parts by weight of distilled water, 5 parts by weight of ethylene glycol and 5 parts by weight of ethyl alcohol were stirred and mixed with a supermill dispersing machine (Inoue Seisakusho), Then, it was filtered through a 0.5 / m filter to produce ink. The viscosity of this ink was 2.8 cp at 20 ° C, and the pigment concentration was 4% by weight.
実施例 2 Example 2
硬化性モノマーをイ ンクに包含させるこ とによる効果を調べるた めに、 実施例 1 で製造した分散イ ンク A 5 0重量部、 TM P T A 4 8重量部、 ベンゾフ エ ノ ン 2重量部をスー パ ー ミ ル分散機 （井上製 作所） で攪拌混合し、 その後、 0. 5 mのフ ィ ルターで濾過して イ ンクを製造した。 このイ ンクの粘度は 2 0 °Cにおいて 2. 1 c p であり、 顔料濃度は 4重量％であった。  In order to examine the effect of including the curable monomer in ink, 50 parts by weight of the dispersed ink A, 8 parts by weight of TM PTA, and 2 parts by weight of benzophenone prepared in Example 1 were mixed with soot. The mixture was stirred and mixed with a parmill disperser (Inoue Seisakusho), and then filtered through a 0.5 m filter to produce ink. The viscosity of this ink was 2.1 cp at 20 ° C, and the pigment concentration was 4% by weight.
比較例 1 Comparative Example 1
温度制御装置と接続したビーズミ ルに、 4 0 °Cにおいて、 水 9 2 g及び実施例 1 で用いたのと同一の顔料 8 gを加え、 粒径が 0. 5 〃 m以下になるまで約 1 5分間分散させた。 このように製造したィ ンクを分散ィ ンク B と呼ぶ。 In a bead mill connected to a temperature controller, at 40 ° C, water 92 g and 8 g of the same pigment used in Example 1 were added and dispersed for about 15 minutes until the particle size became 0.5 μm or less. The ink manufactured in this way is called distributed ink B.
上記の分散イ ンク B 5 0重量部、 蒸留水 4 0重量部、 ジエチレン グリ コール 5重量部及びエチルアルコール 5重量部をスー パ ー ミ ル 分散機 （井上製作所） で攬拌混合し、 その後 0. 5 /i mのフ ィ ルタ —で濾過してイ ンクを製造した。 このイ ンクの粘度は 2 0 °Cにおい て 1 , 8 c pであり、 顔料濃度は 4 重量％であった。  50 parts by weight of the above dispersion ink B, 40 parts by weight of distilled water, 5 parts by weight of diethylene glycol and 5 parts by weight of ethyl alcohol were mixed with a supermill dispersing machine (Inoue Seisakusho), followed by mixing by stirring. The ink was prepared by filtration through a 5 / im filter. The viscosity of this ink was 1.8 cp at 20 ° C, and the pigment concentration was 4% by weight.
試験方法 Test method
*使用環境下での試験 （試験 1 )  * Test under operating environment (Test 1)
上記のように製造した実施例 1 及び比較例 1 の試料を、 それぞれ 、 サンプル瓶中、 5 °C及び 4 0 °Cで 3 力月間保存した。  The samples of Example 1 and Comparative Example 1 produced as described above were stored in sample bottles at 5 ° C. and 40 ° C. for three months, respectively.
*梱包環境での保存試験 （試験 2 ) * Storage test in a packaging environment (Test 2)
各試料をそれぞれサンブル瓶中、 一 5 °C〜 7 0 °Cで 3 力月保存し た。  Each sample was stored for 3 months at 15 ° C to 70 ° C in a sample bottle.
以下の試験 3〜 6 に関しては F M J P 2 0 1 (富士通 （株） 製） のサーマルイ ンク ジヱ ッ ト方式のジエ ツ トプリ ンターを用いて行つ た。 実施例 2で製造したイ ンクについては紫外線ラ ンプを使用 して 1 0 m w / c m 2 の強度で 1 秒間硬化させた。 The following tests 3 to 6 were performed using a thermal ink jet type jet printer of FMJP 201 (manufactured by Fujitsu Limited). The ink produced in Example 2 was cured for 1 second at an intensity of 10 mw / cm 2 using an ultraviolet lamp.
*吐出安定性 （試験 3 ) * Discharge stability (Test 3)
室温 （ 2 5 °C) 、 5 °C及び 4 0 °Cで、 それぞれ 1 0 0 0枚の連続 吐出を行い、 記録安定性を測定した。  At room temperature (25 ° C.), 5 ° C. and 40 ° C., 10000 sheets were continuously ejected, and the recording stability was measured.
*印字濃度 （試験 4 ) * Print density (Test 4)
市販の再生紙 （ゼロ ッ クス社製 WR紙） に印字して試験片と し、 マクべス濃度計で測定した。  Test pieces were printed on commercially available recycled paper (WR paper manufactured by Xerox Corporation) and measured with a Macbeth densitometer.
*印字品質 （試験 5 ) * Print quality (Test 5)
上記の再生用紙に、 1 ドッ ト印字を行ったときの ドッ ト径の広が り （滲み） と ドッ 卜の真円度を光学顕微鏡で判定した。 Dot diameter increases when 1-dot printing is performed on the above recycled paper. The bleeding and the roundness of the dot were determined with an optical microscope.
*印字定着性 （試験 6 ) * Print fixability (Test 6)
印字された直後の用紙を、 同じ用紙で擦ったときの汚れを目視で 判断した。  Stain when the paper immediately after printing was rubbed with the same paper was visually judged.
試験番号 実施例 1 実施例 2 比較例 1Test number Example 1 Example 2 Comparative example 1
1 ◎ 〇 X1 ◎ 〇 X
2 〇 〇 X2 〇 〇 X
3 ◎ ◎ X3 ◎ ◎ X
4 1 . 2 1 . 2 0 . 94 1 .2 1 .2 0 .9
5 ◎ ◎ X5 ◎ ◎ X
6 〇 ◎ X 注 ： 判定は次の基準によつた。 6 〇 ◎ X Note: Judgment was based on the following criteria.
試験 1及び 2 Test 1 and 2
記録液の液分離及び沈降なし…◎ No separation and sedimentation of recording liquid… ◎
記録液の液分離が若干あるが、 沈降は認められず、 弱い振動で元に 戻る…〇 There is some separation of the recording liquid, but no sedimentation is observed, and the liquid returns to the original state with a slight vibration… 〇
記録液の液分離及び沈降が認められ、 弱い振動では元に戻らない ·· X Separation and sedimentation of the recording liquid are observed, and cannot be restored by weak vibration. X
sA, ¾j 3 sA, ¾j 3
安定な吐出…◎ Stable discharge… ◎
吐出に乱れがある… X Discharge is disturbed ... X
試 5 Trial 5
滲みが少なく真円度が高い…◎ Less bleeding and high roundness… ◎
滲みが多く真円度が低い… X A lot of bleeding and low roundness ... X
si ¾ 6 si ¾ 6
汚れがない…◎ No dirt ... ◎
印字は良好であつたが、 全面塗りで少し汚れる…〇 印字周辺部が汚れる… X The printing was good, but the whole surface was slightly stained ... 〇 The periphery of the print becomes dirty ... X
実施例では富士通のサ一マル式のイ ンク ジヱ ッ トプリ ンターを使 用 したが他のサ一マル式のプリ ンター及びピエゾ式イ ンク ジヱ ッ 卜 プリ ンターでも同様の結果を得られる ものと考えられる。 産業上の利用可能性  In the embodiment, Fujitsu's general-purpose ink jet printer was used, but similar results can be obtained with other thermal printers and piezo-type ink jet printers. it is conceivable that. Industrial applicability
イ ソブチレン無水マレイ ン酸共重合樹脂のような水に不溶性又は 難溶性で且つ親水性の高分子材料を使用する と、 それにより コー ト された顔料の水性分散液が安定性を有し、 且つ、 印刷時には、 前記 高分子材料の粘着性により、 媒体 （紙） への定着性を向上させるこ とができる。  When a water-insoluble or poorly-soluble and hydrophilic polymer material such as isobutylene maleic anhydride copolymer resin is used, an aqueous dispersion of the coated pigment has stability, and At the time of printing, the fixability to a medium (paper) can be improved due to the adhesiveness of the polymer material.
紫外線硬化性モノ マー若し く はオリ ゴマーを含ませることによ り 、 イ ン ク全体と しての粘度を低く することができ、 且つ、 紫外線を 照射しないかぎり硬化しないことからへッ ド上での目詰ま りを生じ ることがない。  By including an ultraviolet-curable monomer or oligomer, the viscosity of the ink as a whole can be reduced, and it will not cure unless irradiated with ultraviolet light. No clogging occurs.
染料ィ ンクの代わりに顔料系ィ ンクを使用するこ とにより耐水性 、 耐光性に優れた顔料イ ンクで印刷する こ とができる。  By using a pigment ink instead of a dye ink, printing can be performed with a pigment ink having excellent water resistance and light fastness.

Claims

請 求 の 範 囲 The scope of the claims
1 . 水、 顔料、 及び、 水に不溶性又は難溶性で且つ親水性の高分 子材料からなり、 前記顔料が前記水に不溶性又は難溶性で且つ親水 性の高分子材料により コ ー 卜されているこ とを特徴とするイ ン ク ジ エ ツ トプリ ンター用イ ンク。 1. It is composed of water, a pigment, and a polymer material that is insoluble or hardly soluble in water and hydrophilic, and the pigment is coated with the polymer material that is insoluble or hardly soluble in water and hydrophilic. Ink for an inkjet printer.
2 . 紫外線硬化性モ ノ マー若し く はオ リ ゴマーの分散体を更に含 む請求の範囲 1 記載のイ ンク ジヱ ッ トプリ ンタ一用イ ンク。  2. The ink for an ink jet printer according to claim 1, further comprising a dispersion of a UV-curable monomer or an oligomer.
3 . 前記高分子材料がィ ソブチレン無水マレイ ン酸共重合樹脂、 共重合ナイ ロ ン、 ポリ ビニルイ ソブチルエーテルおよびポ リ ビニル ェチルエーテルからなる群より選ばれた材料である請求の範囲 1 ま たは 2 のいずれか 1 項記載のィ ンク ジヱ ッ トプリ ンタ一用イ ンク。  3. The method according to claim 1, wherein the polymer material is a material selected from the group consisting of isobutylene maleic anhydride copolymer resin, copolymerized nylon, polyvinylisobutyl ether, and polyvinyl ethyl ether. An ink jet printer ink according to any one of the above.
4 . 前記顔料がカーボンブラ ッ ク、 アルミ ナ、 硫酸バリ ウム、 黄 鉛およびチタ ンホワイ トからなる群より選ばれた合成無機顔料であ る請求の範囲 1 または 2のいずれか 1 項記載のィ ンク ジヱ ッ トプリ ンター用イ ンク。  4. The method according to claim 1, wherein the pigment is a synthetic inorganic pigment selected from the group consisting of carbon black, alumina, barium sulfate, graphite, and titanium white. Ink for ink jet printer.
5 . 前記顔料がァ ゾ顔料、 塩基性染料からのレーキ顔料およびフ タロ シアニ ン顔料からなる群より選ばれた合成有機顔料である請求 の範囲 1 または 2 のいずれか 1 項記載のィ ンク ジヱ ッ トプリ ンター 用イ ン ク 。  5. The ink according to claim 1, wherein the pigment is a synthetic organic pigment selected from the group consisting of azo pigments, lake pigments from basic dyes, and phthalocyanine pigments.ヱ Ink for the print printer.
6 . 前記顔料が金属またはその酸化物である請求の範囲 1 または 2 のいずれか 1 項記載のイ ンク ジ ヱ ッ トプリ ンター用イ ンク。  6. The ink for an ink jet printer according to claim 1, wherein the pigment is a metal or an oxide thereof.
7 . 前記顔料がイ ンク重量基準で 20 %までの量で含まれている請 求の範囲 4記載のイ ンク ジエ ツ トプリ ンタ一用イ ンク。  7. The ink for an inkjet printer according to claim 4, wherein said pigment is contained in an amount of up to 20% based on the weight of the ink.
8 . 前記顔料がィ ン ク重量基準で 1 0 %までの量で含まれている請 求の範囲 5記載のイ ンク ジヱ ッ トプリ ンター用イ ンク。  8. The ink for an ink jet printer according to claim 5, wherein the pigment is contained in an amount of up to 10% based on the weight of the ink.
9 . 前記顔料の粒子サイズが 0. 0 1〜 1 ミ ク ロ ンである請求の範囲 1 または 2のいずれか 1項記載のイ ンク ジエ ツ トプリ ンタ 用イ ン り。 9. The claim wherein the pigment has a particle size of 0.01 to 1 micron. The ink jet printer printer according to any one of the items 1 or 2.
10. 前記紫外線硬化性モノ マ一またはオリ ゴマーが  10. The UV-curable monomer or oligomer is
0  0
II II
CH20CCH= CH2 CH 2 0CCH = CH 2
0  0
II II
CH2CH2— C一 CH20CCH= CH2 CH 2 CH 2 — C-CH 2 0 CCH = CH 2
I I
CH20CCH= CH2 CH 2 0CCH = CH 2
!1  ! 1
0  0
CH20R CH20R CH 2 0R CH 2 0R
I I  I I
R0CH2— C— CH2— 0—CH2— C— CH20R R0CH 2 — C— CH 2 — 0—CH 2 — C— CH 2 0R
I I CH20R CH20R II CH 2 0R CH 2 0R
(上式中、 Rが全てァク リ ロイルである化合物と Rのう ちの 5個が ァク リ ロイルであり且つ Rのうちの 1 個がヒ ドロキシである化合物 の混合物である力、、 Rのうちの 5個がァク リ ロイルであり且つ尺の うちの 1個がアルキノ ィルである力、、 または Rのう ちの 3個がァク リ ロイルであり且つ Rのうちの 3個がアルキノ ィルである。 ） および  (Wherein R is a mixture of a compound in which R is all acryloyl and a compound in which 5 of Rs are acryloyl and one of R is hydroxy, R Five of which are acryloyl and one of the scales is an alkynyl, or three of R are acryloyl and three of R are Alkynyl.) And
0  0
II II
CH2 = CHC0CH2 CH 2 = CHC0CH 2
CH3— C一 CH3 CH3 0 CH 3 — C-CH 3 CH 3 0
I I II I I II
CHz0C- C- CH2 = CHCOCH, CH z 0C- C- CH 2 = CHCOCH,
II I  II I
0 CH3 0 CH 3
からなる群より選ばれたモノ マー若し く はそのオ リ ゴマ一である請 求の範囲 2記載のイ ンク ジヱ ッ トプリ ンタ一用イ ンク。 An ink for an ink jet printer according to claim 2, which is a monomer or an oligomer selected from the group consisting of:
PCT/JP1996/000696 1995-03-15 1996-03-15 Pigment ink for ink jet printer WO1996028518A1 (en)

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GB9623811A GB2303376B (en) 1995-03-15 1996-03-15 Pigment-containing ink for ink-jet printers
DE19680301T DE19680301C2 (en) 1995-03-15 1996-03-15 Pigment-based ink for inkjet printers

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JP4281289B2 (en) * 2002-04-16 2009-06-17 コニカミノルタホールディングス株式会社 Method for producing actinic ray curable ink
ES2200711B2 (en) * 2002-08-27 2005-12-16 Chimigraf Iberica, S.L. PROCEDURE FOR THE MANUFACTURE OF A DIGITAL PRINTING INK AND OBTAINED INK.
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GB9623811D0 (en) 1997-01-08
JP3625479B2 (en) 2005-03-02

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